Classifications

• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B33/00—Silicon; Compounds thereof
  • C01B33/113—Silicon oxides; Hydrates thereof
  • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
  • C01B33/126—Preparation of silica of undetermined type
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C11/00—Multi-cellular glass ; Porous or hollow glass or glass particles
  • C03C11/002—Hollow glass particles
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
  • C03B19/00—Other methods of shaping glass
  • C03B19/10—Forming beads
  • C03B19/108—Forming porous, sintered or foamed beads
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
  • C03B19/00—Other methods of shaping glass
  • C03B19/10—Forming beads
  • C03B19/109—Glass-melting furnaces specially adapted for making beads
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
  • C03C1/002—Use of waste materials, e.g. slags
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C11/00—Multi-cellular glass ; Porous or hollow glass or glass particles
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
  • C04B14/02—Granular materials, e.g. microballoons
  • C04B14/04—Silica-rich materials; Silicates
  • C04B14/22—Glass ; Devitrified glass
  • C04B14/24—Glass ; Devitrified glass porous, e.g. foamed glass
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
  • C04B20/0016—Granular materials, e.g. microballoons
  • C04B20/002—Hollow or porous granular materials
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
  • C04B20/02—Treatment
  • C04B20/04—Heat treatment
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
  • C04B20/02—Treatment
  • C04B20/04—Heat treatment
  • C04B20/06—Expanding clay, perlite, vermiculite or like granular materials
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
  • C04B20/02—Treatment
  • C04B20/04—Heat treatment
  • C04B20/06—Expanding clay, perlite, vermiculite or like granular materials
  • C04B20/066—Expanding clay, perlite, vermiculite or like granular materials in shaft or vertical furnaces
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
  • C04B20/02—Treatment
  • C04B20/04—Heat treatment
  • C04B20/06—Expanding clay, perlite, vermiculite or like granular materials
  • C04B20/068—Selection of ingredients added before or during the thermal treatment, e.g. expansion promoting agents or particle-coating materials
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
  • C04B20/10—Coating or impregnating
  • C04B20/1055—Coating or impregnating with inorganic materials
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
  • C04B20/10—Coating or impregnating
  • C04B20/1055—Coating or impregnating with inorganic materials
  • C04B20/1077—Cements, e.g. waterglass
  • C04B20/1085—Waterglass
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F27—FURNACES; KILNS; OVENS; RETORTS
  • F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
  • F27B3/00—Hearth-type furnaces, e.g. of reverberatory type; Tank furnaces
  • F27B3/06—Hearth-type furnaces, e.g. of reverberatory type; Tank furnaces with movable working chambers or hearths, e.g. tiltable, oscillating or describing a composed movement
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F27—FURNACES; KILNS; OVENS; RETORTS
  • F27M—INDEXING SCHEME RELATING TO ASPECTS OF THE CHARGES OR FURNACES, KILNS, OVENS OR RETORTS
  • F27M2003/00—Type of treatment of the charge
  • F27M2003/09—Expanding the charge, e.g. clay
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
  • Y02W30/00—Technologies for solid waste management
  • Y02W30/50—Reuse, recycling or recovery technologies
  • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

• the present disclosure concerns an expandable silica particle, a method for expanding silica particles, expanded silica particles produced by the method, use of expanded silica particles and a method for producing an expandable silica particle.
• Expanded silica particles are utilized in various areas, for example as a filler in matrix materials, like concrete or epoxy, as insulation material with various binder materials, or as water filtration medium.
• matrix materials like concrete or epoxy
• expansion material with various binder materials, or as water filtration medium.
• advantageous physical properties are associated with expanded silica particles, such as low density, high dimensional stability, excellent compression strength, and high insulation capacity.
• Expanded silica particles added to a matrix material may also improve the processability of the matrix material before hardening, for instance by improving flowability at very low water adsorption. Additionally, expanded silica particles may reduce overall material costs, in particular for expensive matrix materials.
• expanded silica materials contribute to environmental sustainability.
• kaolin transfers into metakaolin at temperatures close to the plastic-molten transition and may thereby lose most of its properties as a release agent.
• the metakaolin may also melt into the surface of the softened expanding silica particles, thereby further reducing its effectiveness as a release agent.
• the interior cell walls may rupture, leading to an open-pored internal structure, whereas cells at the outer surface of the expanding silica particles may collapse.
• the surface of the expanding silica particles may additionally become more brittle, leading to a further risk of collapse of cells at the outer surface and consequently a deterioration in physical properties.
• a high adsorption capacity may cause the expanded silica particles to adsorb large quantities of the matrix material.
• Such an adsorption of matrix material negatively affects the properties of the expanded silica particles as a filler material.
• adsorbing concrete additives such as a water reducer, air entrainment agent, will have significant impact on flow behavior and mechanical properties in the cured state. This counteracts the desired effect of lowering the overall material density of matrix and filler.
• the present disclosure concerns an expandable silica particle according to claim 1 and a method for producing expandable silica particles according to claim 8.
• the present disclosure also concerns a method for producing expanded silica particles according to claim 10, an expanded silica particle according to claim 13 and the use of expanded silica particles according to claim 14.
• Figure 1 schematically shows a furnace for the heating of expandable silica particles according to the disclosure.
• An expandable silica particle according to the disclosure comprises silica powder, silica fume, and at least one expanding agent.
• the expandable silica particle further comprises a coating provided on the outer surface of the expandable silica particle, wherein the coating comprises kaolin powder and talc powder.
• kaolin acts as a release agent, whereas talc offsets the negative effects of kaolin at high temperatures by rendering the outer surface of the expanding silica particle more elastic and with closed cells.
• the expandable silica particle may comprise further additives, such as a coloring agent.
• the expandable silica particle may have a bulk density of 0.3 - 1.7 kg/I, preferably 0.5 - 1.5 kg/I.
• the expandable silica particle may have a diameter of 0.1 - 40 mm, preferably 0.25 - 5.6 mm, most preferably 0.8 - 1.6 mm.
• the expandable silica particle comprises 50 - 98 wt% of silica powder.
• the particles of the silica powder may have a diameter of 0.01 - 700 pm.
• the silica powder comprises a recycled glass powder.
• Recycled glass powder may, for instance, be sourced from post-consumer recycled glass, soda lime glass, float glass, windscreens, solar panels.
• the expandable silica particles thereby form an environmentally friendly material.
• the expandable silica particle may comprise 0.85 - 10 wt% of at least one expanding agent.
• the expanding agent may comprise a powder.
• the particles of the expanding agent powder have a diameter of 0.01 - 40.0 pm.
• the at least one expanding agent may comprise aluminum nitride (AIN), silicon carbide (SiC), manganese dioxide (MnCte), sodium carbonate (NasCC ), calcium sodium carbonate (CaNasCC ) or combinations thereof.
• the at least one expanding agent comprises silicon carbide powder.
• the expandable silica particle may comprise 0.01 - 10 wt% of silica fume.
• Silica fume comprises ultrafine silica particles with a particle diameter below 1 pm.
• the diameter of the silica fume particles is around 150 nm.
• the silica fume strengthens the walls of the cells that are formed in the expandable silica particle during expansion. Thereby, rupturing of the cell walls during expansion is reduced. Due to the strengthened cell walls and due to the reduced occurrence of rupturing of cell walls, the resulting expanded silica particle has a higher strength and a higher crush resistance with significantly reduced water adsorption.
• the coating may comprise 0.5 - 10 wt% of kaolin powder (Al 2 Si05(H0) 4 ).
• the kaolin acts as a release agent.
• the coating further comprises talc powder (Mg3SUOio(OH)2).
• the coating may comprise 0.5 - 5 wt% of talc powder.
• the talc powder melts into the surface of the expanding silica particle and renders the surface more elastic or flexible, thereby reducing the collapse of cells at the outer surface of the expanding silica particle. Consequently, the talc powder counteracts the adverse effect of kaolin, occurring at high temperatures, and acts to maintain the surface integrity of the expanding silica particle. Thereby, the resistance against fluid adsorption in the expanded silica particle is improved.
• a method for preparing one or more expandable silica particles according to the disclosure is next described. The method comprises providing expandable silica pre-particles comprising silica powder, silica fume and at least one expanding agent.
• Providing expandable silica pre-particles may comprise the sintering or heat-pressing of a mixture of silica powder, silica fume and at least one expanding agent into a block at a temperature below the activation temperature of the at least one expanding agent.
• the block may then be divided into expandable silica pre-particles, for instance by cutting or by crushing the sintered block into granules.
• the granules may be filtered according to size and large granules may be subjected to further dividing.
• the mixture of silica powder, silica fume and at least one expanding agent may be heat-pressed directly into expandable silica pre particles.
• the mixture of silica powder, silica fume and at least one expanding agent may be provided with a binder and processed in an industrial pelletizer.
• the method for preparing one or more expandable silica particles further comprises the step of coating the outer surface of the expandable silica pre-particle with a coating comprising kaolin and talc, to thereby form an expandable silica particle.
• a method for producing expanded silica particles comprises providing a plurality of expandable silica particles according to the disclosure and heating the expandable silica particles in a chamber 2 of a furnace 1 to above the activation temperature of the expanding agent to form expanded silica particles.
• the expandable silica particles may be fed into the chamber 2 (schematically shown in fig. 1 ) by a feeding system.
• the expandable silica particles may be fed onto an angled, vibrating plate body.
• a directional, high frequent motion may thereby be induced in the expandable silica particles, wherein the motion may be chaotic or turbulent.
• the expandable silica particles may first be fed into a preheating chamber, before being fed or conveyed into the chamber 2.
• the temperature difference between the core and the surface of the expandable silica particles are minimized during preheating.
• the expandable silica particles are heated to above the activation temperature of the expanding agent, to a temperature of 560 - 950°C, preferably 850 - 900°C.
• the expandable silica particles are softened.
• an exotherm reaction occurs, driving expansion of the softened particles.
• the coating on the outer surface of the expandable silica particles isolates the outer surface during exotherm-driven expansion. Thereby, the expansion process is counteracted at the surface of the expanding silica particles, resulting in a denser outer surface of the expanded silica particles, with less open cells as compared to particles without coating.
• the temperature and the residence time may be controlled, thereby controlling the expansion rate of the expandable silica particles.
• the residence time may be controlled by controlling the conveying speed of the particles in the chamber 2.
• the furnace 1 may further comprise a vibration plate 3, forming the bottom of the chamber 2.
• the vibration plate 3 is preferably inclined by an inclination angle with respect to the horizontal direction, from the entry downward to the exit of the furnace.
• the vibration plate 3 is vibrated during the heating and expansion of the expandable silica particles, thereby inducing motion in the expandable silica particles.
• the contact time between silica particles in the furnace 1 is thereby limited, such that the risk for adhesion of particles to one another and to the furnace is minimized.
• the expanded silica particles may enter a cooling zone, comprising one or more stages kept at progressively lower temperatures.
• the expanded silica particles are preferably cooled to ambient temperature in the cooling zone, allowing further handling of the expanded silica particles.
• the temperature and the residence time for each stage may be controlled, thereby controlling the cooling rate of the expanded silica particles.
• internal tension within the expanded silica particles due to differential cooling rates at the particle surface and in the particle-interior may thereby be minimized.
• the expanded silica particles may be coated with a sodium silicate solution, also known as water glass, preferably at a temperature of 0.1 - 200°C.
• the sodium silicate solution further reduces surface porosity of the expandable silica particle, thereby improving resistance against fluid adsorption in the expanded silica particle.
• An expanded silica particle according to the disclosure preferably has a bulk density of 150 - 900 g/l.
• the expanded silica particle has a spherical or close to spherical shape.
• the expanded silica particle may be used as a filler in concrete, plaster, gypsum, mortar, epoxy, polyurethane, acrylate or a suitable organic binder, or artificial turf or as a filler in water filtration cartridges.
• the expanded silica particle has a significantly reduced fluid adsorption capacity and may, for instance, adsorb a negligible amount of concrete additives when used as a filler in a concrete matrix material.
• Expandable silica pre-particles were provided by sintering 95 wt% of silica powder, 3 wt% of SiC powder expanding agent and 2 wt % of silica fume at 710°C into a block.
• the silica powder comprises recycled flat glass.
• the SiC powder had a particle diameter of 0.01 - 2 pm.
• the sintered block was then crushed into expandable pre-particles, which were filtered according to particle diameter.
• the expandable pre-particles were dry-coated with a coating comprising kaolin powder and talc powder, to form expandable silica particles.
• the expandable silica particles comprised 91.2 wt% of silica powder, 2.88 wt% of SiC powder, 1.92 wt % of silica fume, 2 wt% kaolin powder and 2 wt% talc powder.
• the expandable silica particles were preheated at 680°C for a period of 300 s, before being heated to 870°C for 36 s. Heating was then continued at 865°C for 45 s and at 860°C for 45 s, before cooling commenced, at 200°C for 18 s.
• the resulting expanded silica particles had a bulk density (determined according to UNI EN 1097-6:2013, appendix C) of 275 g/l and a diameter (determined according to sieving method of UNI EN 933-1 : 2012) of 2 - 8 mm.
• Water adsorption determined according to UNI EN 1097-6:2013 (appendix C - adsorption after 5 minutes) was measured to be 4.4%.
• Expandable silica pre-particles were provided by sintering 97 wt% of silica powder and 3 wt% of SiC powder expanding agent at 710°C into a block.
• the silica powder comprised recycled flat glass.
• the SiC powder had a particle diameter of 0.01 - 2 pm.
• the sintered block was then crushed into expandable pre-particles, which were filtered according to particle diameter.
• the expandable pre-particles were then dry-coated with a coating comprising kaolin powder, to form expandable silica particles.
• the expandable silica particles comprised 93.12 wt% of silica powder, 2.88 wt% of SiC expanding agent and 4 wt% of kaolin coating.
• the expandable silica particles were heated and cooled according to the same regime as in Example 1. Bulk density, particle diameter, water adsorption and crushing resistance were determined according to the same standards as cited for Example 1.
• the resulting expanded silica particles had a particle diameter of 2 - 8 mm, a bulk density of 300 g/l for the segment with particle diameters of 2 - 4 mm and a bulk density of 275 g/l for the segment with particle diameters of 4 - 8 mm.
• the expanded silica particles had a water adsorption of 24.2 % for the segment with particle diameters of 2 - 4 mm and of 21 ,9% for the segment with particle diameters of 4 - 8 mm.
• the expanded silica particles in the comparative example had a crushing resistance of 3.5 N/mm 2 for the segment with particle diameters of 2 - 4 mm and of 2.7 N/mm 2 for the segment with particle diameters of 4 - 8 mm.

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